Bio-derived cross-linkers

ABSTRACT

A process includes utilizing biorenewable cis-3-hexenol to form a bio-derived cross-linker and utilizing the bio-derived cross-linker to form a cross-linked polymeric material.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation application of U.S. patentapplication Ser. No. 15/410,025, filed Jan. 19, 2017.

BACKGROUND

Polydimethylsiloxane (PDMS) is among the most widely used silicon-basedpolymers, and the most widely used organic silicon-based polymer. PDMSmaterials have a wide range of applications including contact lenses,medical devices, soft lithography processes, shampoos, caulking, andlubricants (among other alternatives). One reason for the wide-rangingapplications for PDMS materials is the variety of ways in which theproperties of PDMS may be controlled through polymer cross-linking. Byemploying PDMS and small organic molecules with different organicfunctional groups, many possibilities exist for different PDMS materialsto be cross-linked in different ways.

SUMMARY

According to an embodiment, a process of forming a cross-linkedpolymeric material is disclosed. The process includes utilizingbiorenewable cis-3-hexenol to form a bio-derived cross-linker. Theprocess also includes utilizing the bio-derived cross-linker to form thecross-linked polymeric material.

According to another embodiment, a cross-linked polydimethylsiloxane(PDMS) material is disclosed. The cross-linked PDMS material is formedby a process that comprises chemically reacting a functionalized PDMSmaterial with a bio-derived cross-linker that is derived frombiorenewable cis-3-hexenol.

According to another embodiment, a process of forming a bio-derivedcross-linker is disclosed. The process includes initiating a firstchemical reaction to form hexane-1,3,4-triol from biorenewablecis-3-hexenol. The process also includes initiating a second chemicalreaction to form a bio-derived cross-linker from the hexane-1,3,4-triol.

The foregoing and other objects, features, and advantages of theinvention will be apparent from the following more particulardescriptions of exemplary embodiments of the invention as illustrated inthe accompanying drawings wherein like reference numbers generallyrepresent like parts of exemplary embodiments of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chemical reaction diagram illustrating a process of forminga cross-linked PDMS material using a first bio-derived cross-linkingmaterial that is formed from the biorenewable molecule cis-3-hexenol,according to one embodiment.

FIG. 2 is a chemical reaction diagram illustrating a process of forminga cross-linked PDMS material using the first bio-derived cross-linkingmaterial of FIG. 1, according to one embodiment.

FIG. 3 is a chemical reaction diagram illustrating a process of forminga cross-linked PDMS material using a second bio-derived cross-linkingmaterial that is formed from the biorenewable molecule cis-3-hexenol,according to one embodiment.

FIG. 4 is a chemical reaction diagram illustrating a process of forminga cross-linked PDMS material using a third bio-derived cross-linkingmaterial that is formed from the biorenewable molecule cis-3-hexenol,according to one embodiment.

FIG. 5 is a chemical reaction diagram illustrating a process of forminga cross-linked PDMS material using the third bio-derived cross-linkingmaterial of FIG. 4, according to one embodiment.

FIG. 6 is a chemical reaction diagram illustrating a process of forminga cross-linked PDMS material using a fourth bio-derived cross-linkingmaterial that is formed from the biorenewable molecule cis-3-hexenol,according to one embodiment.

FIG. 7 is a chemical reaction diagram illustrating a process of forminga cross-linked PDMS material using a fifth bio-derived cross-linkingmaterial that is formed from the biorenewable molecule cis-3-hexenol,according to one embodiment.

FIG. 8 is a chemical reaction diagram illustrating a process of forminga cross-linked PDMS material using a sixth bio-derived cross-linkingmaterial that is formed from the biorenewable molecule cis-3-hexenol,according to one embodiment.

FIG. 9 is a chemical reaction diagram illustrating a process of forminga bio-derived cross-linked polymeric material from the sixth bio-derivedcross-linking material of FIG. 8, according to one embodiment.

FIG. 10 is a flow diagram showing a particular embodiment of a processof forming a bio-derived cross-linker from the biorenewable moleculecis-3-hexenol.

FIG. 11 is a flow diagram showing a particular embodiment of a processof utilizing a bio-derived cross-linker that is formed from thebiorenewable molecule cis-3-hexenol to form a cross-linked polymericmaterial.

DETAILED DESCRIPTION

The present disclosure describes cross-linkers derived from thebiorenewable molecule cis-3-hexenol and methods of forming bio-derivedcross-linkers from the biorenewable molecule cis-3-hexenol. Thebiorenewable molecule cis-3-hexenol, also referred to herein as naturalleaf alcohol, may be extracted from plants, where it is formed fromenzymatic oxidation of fatty acids (e.g., linoleic acid). In some cases,the biorenewable molecule cis-3-hexenol may be used to formhexane-1,3,4-triol, which may subsequently be utilized as across-linking material. In other cases, the bio-derivedhexane-1,3,4-triol material may undergo one or more subsequent chemicalreactions (e.g., with other biorenewable materials) to form alternativebio-derived cross-linking materials. Utilizing biorenewable natural leafalcohol (or derivatives thereof) as a cross-linking material mayincrease the biorenewable content of a cross-linked polymeric material,such as a cross-linked polydimethylsiloxane (PDMS) material, for use invarious applications.

The bio-derived cross-linkers of the present disclosure may be appliedto PDMS (or other polymers such as PE, PP, PC, PU, acrylics, etc.) fordifferent applications. In some cases, curing may be performed duringprocessing of a desired material, with a completely cross-linkedpolymer. In other cases, the cross-linkers may be mixed with PDMS, butleft in a partial or uncross-linked state that can be left to cross-linkupon addition to the PDMS for a particular desired application (e.g., acaulking or coating application, among other alternatives).

Referring to FIG. 1, a chemical reaction diagram 100 illustrates aprocess of forming a bio-derived cross-linker from the biorenewablemolecule cis-3-hexenol and utilizing the bio-derived cross-linker toform a cross-linked polymeric material, according to one embodiment. InFIG. 1, cis-3-hexenol (which may be derived from natural leaf alcohol)is converted to hexane-1,3,4-triol, which is then utilized as a firstbio-derived cross-linker (designated as “Bio-Derived Cross-Linker(1)” inFIG. 1) for polymeric cross-linking. In the particular embodimentdepicted in FIG. 1, the first bio-derived cross-linker is used to form across-linked polydimethylsiloxane (PDMS) material (designated as“Cross-Linked PDMS Material(1)” in FIG. 1). The cross-linked PDMSmaterial illustrated in FIG. 1 may be formed via a chemical reaction(e.g., a condensation cure reaction) of the first bio-derivedcross-linker and a PDMS polymer.

In the first chemical reaction depicted at the top of FIG. 1,cis-3-hexenol (which may be may be extracted from plants) is convertedto hexane-1,3,4-triol via Sharpless Asymmetric Dihydroxylation. As aprophetic example, a reaction vessel may be charged with cis-3-hexenol(1.0 equiv.) and dissolved in a solvent mixture that may be 9:1acetone/water or tBuOH/water and may be cooled to 0° C. An oxidant suchas 4-methylmorpholine-N-oxide or potassium ferricyanide (1.5 equiv.) maybe added to reaction mixture, followed by 1 mol % osmium tetroxide. Thereaction mixture may be stirred overnight and may be quenched by theaddition of a saturated sodium sulfite solution, and extracted withethyl acetate (3 x). The combined organic layers may be washed withbrine, dried over magnesium sulfate, filtered, and concentrated invacuo. The crude mixture may be purified by distillation orchromatography.

The second chemical reaction depicted at the bottom of FIG. 1illustrates that the hexane-1,3,4-triol material may be utilized as abio-derived cross-linker to form a cross-linked polymeric material. FIG.1 illustrates a particular embodiment of a condensation cure reactionthat utilizes dibutyltin dilaurate (DBTDL) as a catalyst. FIG. 1 depictsan example in which all three hydroxyl groups of the bio-derivedhexane-1,3,4-triol molecule react in the condensation cure reaction.Depending on the reaction conditions, all three hydroxyl groups may beused to cross-link the PDMS polymer or less than three hydroxyl groupsmay be used for cross-linking. To illustrate, by controlling thereaction conditions, catalyst type (other tin or platinum catalyst maybe used), catalyst loading, and stoichiometry, a fraction of thehydroxyl groups (e.g., less than three hydroxyl groups perhexane-1,3,4-triol molecule, on average) can be used for PDMScross-linking. The ability to control the number of hydroxyl groups thatreact may enable better control of the mechanical properties of thefinal polymer.

As a prophetic example, a hydride-functionalized siloxane may be blendedwith hexane-1,3,4-triol (about 1-20% w/w) and catalyst (DBDTL in thiscase, 0.1%-2.0% w/w) and mixed. The mixture may be applied to molds orcoated onto a substrate and cured for times and temperatures asappropriate for desired applications.

Thus, FIG. 1 illustrates an example of a process of forming abio-derived cross-linker from the biorenewable molecule cis-3-hexenoland utilizing the bio-derived cross-linker to form a cross-linkedpolymeric material. The bio-derived cross-linker may be used to increasethe biorenewable content of a resulting cross-linked polymeric material(e.g., a cross-linked PDMS material).

Referring to FIG. 2, a chemical reaction diagram 200 illustrates aprocess of forming a bio-derived cross-linker from the biorenewablemolecule cis-3-hexenol and utilizing the bio-derived cross-linker toform a cross-linked polymeric material, according to one embodiment. Thebio-derived cross-linker depicted in FIG. 2 corresponds to the firstbio-derived cross-linker depicted in FIG. 1 and may be formed accordingto the process previously described herein with respect to FIG. 1. Inthe particular embodiment depicted in FIG. 2, the first bio-derivedcross-linker is used to form a cross-linked PDMS material (designated as“Cross-Linked PDMS Material(2)” in FIG. 2). The cross-linked PDMSmaterial illustrated in FIG. 2 may be formed via a chemical reaction(e.g., a condensation cure reaction) of the first bio-derivedcross-linker and an alkoxy-functionalized siloxane, such as amethoxy-functionalized siloxane.

The second chemical reaction depicted at the bottom of FIG. 2illustrates that the hexane-1,3,4-triol material may be utilized as abio-derived cross-linker to form a cross-linked polymeric material. FIG.2 illustrates a particular embodiment of a condensation cure reactionthat utilizes DBTDL as a catalyst. As a prophetic example, analkoxy-functionalized siloxane (e.g., a methoxy-functionalized siloxane)may be blended with hexane-1,3,4-triol (about 1-20% w/w) and catalyst(DBDTL in this case, 0.1%-2.0% w/w) and mixed. The mixture may beapplied to molds or coated onto a substrate and cured for times andtemperatures as appropriate for desired applications.

FIG. 2 depicts an example in which all three hydroxyl groups of thebio-derived hexane-1,3,4-triol molecule react in the condensation curereaction. Depending on the reaction conditions, all three hydroxylgroups may be used to cross-link the PDMS polymer or less than threehydroxyl groups may be used for cross-linking. To illustrate, bycontrolling the reaction conditions, catalyst type (other tin orplatinum catalyst may be used), catalyst loading, and stoichiometry, afraction of the hydroxyl groups (e.g., less than three hydroxyl groupsper hexane-1,3,4-triol molecule, on average) can be used for PDMScross-linking. The ability to control the number of hydroxyl groups thatreact may enable better control of the mechanical properties of thefinal polymer.

Thus, FIG. 2 illustrates an example of a process of utilizing thebio-derived cross-linker formed from the biorenewable moleculecis-3-hexenol to form a cross-linked polymeric material. The bio-derivedcross-linker may be used to increase the biorenewable content of aresulting cross-linked polymeric material (e.g., a cross-linked PDMSmaterial).

FIGS. 3 to 8 illustrate examples of other bio-derived cross-linkers thatmay be formed from the biorenewable molecule cis-3-hexenol. While FIGS.3-8 illustrate that the bio-derived cross-linkers may be utilized toform cross-linked PDMS materials, it will be appreciated that thebio-derived materials may be utilized in alternative reactions. Forexample, FIG. 9 illustrates an example in which a bio-derivedcross-linker that includes thiol (or mercapto) groups may form analternative bio-derived cross-linked polymeric material via an oxidationreaction that results in the formation of disulfide linkages.

Referring to FIG. 3, a chemical reaction diagram 300 illustrates aparticular embodiment of a process of utilizing the bio-derivedhexane-1,3,4-triol molecule to form a second bio-derived cross-linker(identified as “Bio-Derived Cross-Linker(2)” in FIG. 3) that includesmultiple vinyl groups. FIG. 3 further illustrates that the secondbio-derived cross-linker may be utilized to form a cross-linkedpolymeric material (e.g., a cross-linked PDMS material), according toone embodiment.

The first chemical reaction depicted at the top of FIG. 3 illustratesthat the bio-derived hexane-1,3,4-triol molecule may be reacted withacrylic acid via an acid- (or base-) catalyzed condensation reaction toform a cross-linker with multiple vinyl groups. The acrylic acid may beformed from biorenewable resource(s).

The second chemical reaction depicted at the bottom of FIG. 3illustrates that the second bio-derived cross-linker may be utilized toform a cross-linked polymeric material. FIG. 3 illustrates a particularembodiment of an addition reaction that utilizes a platinum (Pt)catalyst. As a prophetic example, a hydride-functionalized siloxane maybe blended with the second bio-derived cross-linker having multiplevinyl groups (1-20% w/w) and Pt catalyst, such as Speier's catalyst(H₂PtCl₆) or Karstedt's catalyst (C₂₄H₅₄O₃Pt₂Si₆), and are then mixed.An addition cure reaction via hydrosilation may be performed on themixture.

FIG. 3 depicts an example in which all three vinyl groups of the secondbio-derived cross-linker react in the addition reaction. Depending onthe reaction conditions, all three vinyl groups may be used tocross-link the PDMS polymer or less than three vinyl groups may be usedfor cross-linking. To illustrate, by controlling the reactionconditions, catalyst type (other tin or platinum catalyst may be used),catalyst loading, and stoichiometry, a fraction of the vinyl groups canbe used for PDMS cross-linking. The ability to control the number ofvinyl groups that react may enable better control of the mechanicalproperties of the final polymer.

Thus, FIG. 3 illustrates an example of a process of forming abio-derived cross-linker having multiple vinyl groups fromhexane-1,3,4-triol (derived from the biorenewable moleculecis-3-hexenol) and utilizing the bio-derived cross-linker to form across-linked polymeric material. The bio-derived cross-linker may beused to increase the biorenewable content of a resulting cross-linkedpolymeric material (e.g., a cross-linked PDMS material).

Referring to FIG. 4, a chemical reaction diagram 400 illustrates aparticular embodiment of a process of utilizing the bio-derivedhexane-1,3,4-triol molecule to form a third bio-derived cross-linker(identified as “Bio-Derived Cross-Linker(3)” in FIG. 4) that includesmultiple vinyl groups. FIG. 4 further illustrates that the thirdbio-derived cross-linker may be utilized to form a cross-linkedpolymeric material (e.g., a cross-linked PDMS material), according toone embodiment.

The first chemical reaction depicted at the top of FIG. 4 illustratesthat the bio-derived hexane-1,3,4-triol molecule may be reacted withallyl bromide via a substitution reaction to form a cross-linker withmultiple vinyl groups (that is different from the bio-derivedcross-linker with multiple vinyl groups shown in FIG. 3). In some cases,the allyl bromide may be synthesized in one step from a biorenewableallyl alcohol.

As a prophetic example, cis-3-hexenol may be added to a suspension orsolution of a base (e.g., sodium hydride) in an organic solvent, such astetrahydrofuran (THF) or diethyl ether at 0° C. The reaction mixture maybe stirred for 30 minutes before adding allyl bromide (>3 equiv.),dropwise. The reaction mixture may be stirred for approximately 3 hours,and then neutralized by hydrochloric (HCl) acid. The aqueous and organiclayers may then be separated. The aqueous layer may be extracted withdiethyl ether, and rinsed with brine. The organic layer may be driedover magnesium sulfate (MgSO₄), and the solvent may be removed in vacuo.The residue is purified by distillation or column chromatography

The second chemical reaction depicted at the bottom of FIG. 4illustrates that the third cross-linker may be utilized to form across-linked polymeric material. FIG. 4 illustrates a particularembodiment of an addition reaction that utilizes a platinum (Pt)catalyst. As a prophetic example, a hydride-functionalized siloxane maybe blended with the third bio-derived cross-linker having multiple vinylgroups (1-20% w/w) and Pt catalyst, such as Speier's catalyst (H₂PtCl₆)or Karstedt's catalyst (C₂₄H₅₄O3Pt₂Si₆), and are then mixed. An additioncure reaction via hydrosilation may be performed on the mixture.

FIG. 4 depicts an example in which all three vinyl groups of the secondbio-derived cross-linker react in the addition reaction. Depending onthe reaction conditions, all three vinyl groups may be used tocross-link the PDMS polymer or less than three vinyl groups may be usedfor cross-linking. To illustrate, by controlling the reactionconditions, catalyst type (other tin or platinum catalyst may be used),catalyst loading, and stoichiometry, a fraction of the vinyl groups canbe used for PDMS cross-linking. The ability to control the number ofvinyl groups that react may enable better control of the mechanicalproperties of the final polymer.

Thus, FIG. 4 illustrates an example of a process of forming abio-derived cross-linker having multiple vinyl groups fromhexane-1,3,4-triol (derived from the biorenewable moleculecis-3-hexenol) and utilizing the bio-derived cross-linker to form across-linked polymeric material via an addition reaction. Thebio-derived cross-linker may be used to increase the biorenewablecontent of a resulting cross-linked polymeric material (e.g., across-linked PDMS material).

Referring to FIG. 5, a chemical reaction diagram 500 illustrates aparticular embodiment of a process of utilizing the third bio-derivedcross-linker having multiple vinyl groups of FIG. 4 to form across-linked polymeric material (e.g., a cross-linked PDMS material) viaa peroxide cure reaction.

The second chemical reaction depicted at the bottom of FIG. 5illustrates that the third cross-linker may be utilized to form across-linked polymeric material via a radical cure reaction using aperoxide initiator. As a prophetic example, a Si—CH₃ functional siloxanemay be blended with the third bio-derived cross-linker having multiplevinyl groups (1-20% w/w) and catalyst (e.g., benzoyl peroxide, 0.2%-1.0%w/w) and mixed. The mixture may be applied to molds or coated onto asubstrate and cured for times and temperatures (e.g., 140-160° C., witha post cure of 25-30° C. higher than the initial reaction temperature toremove volatile peroxides) as appropriate for desired applications.

FIG. 5 depicts an example in which all three vinyl groups of the secondbio-derived cross-linker react in the peroxide cure reaction. Dependingon the reaction conditions, all three vinyl groups may be used tocross-link the PDMS polymer or less than three vinyl groups may be usedfor cross-linking. To illustrate, by controlling the reactionconditions, catalyst type, catalyst loading, and stoichiometry, afraction of the vinyl groups can be used for PDMS cross-linking. Theability to control the number of vinyl groups that react may enablebetter control of the mechanical properties of the final polymer.

Thus, FIG. 5 illustrates an example of a process of forming abio-derived cross-linker having multiple vinyl groups fromhexane-1,3,4-triol (derived from the biorenewable moleculecis-3-hexenol) and utilizing the bio-derived cross-linker to form across-linked polymeric material via a peroxide cure reaction. Thebio-derived cross-linker may be used to increase the biorenewablecontent of a resulting cross-linked polymeric material (e.g., across-linked PDMS material).

Referring to FIG. 6, a chemical reaction diagram 600 illustrates aparticular embodiment of a process of utilizing the bio-derivedhexane-1,3,4-triol molecule to form a fourth bio-derived cross-linker(identified as “Bio-Derived Cross-Linker(4)” in FIG. 6) that includesmultiple acetate groups. FIG. 6 further illustrates that the bio-derivedcross-linker may be utilized to form a cross-linked polymeric material(e.g., a cross-linked PDMS material), according to one embodiment.

The first chemical reaction depicted at the top of FIG. 6 illustratesthat the bio-derived hexane-1,3,4-triol molecule may be reacted withacetic acid or acetic anhydride via an acylation reaction to form across-linker that includes multiple acetate groups. The acetic acid maybe obtained from renewable sources, and acetic anhydride can besynthesized from acetic acid.

As a prophetic example, hexane-1,3,4-triol (1 equiv.), acetic acid oracetic anhydride (4.5-5.0 equiv.), catalytic p-toluenesulfonic acid (orother catalysts such as sulfonic acids, sulfuric acid, phosphoric acid,hydrogen sulfates, dihydrogen phosphates, phosphonic acid esters, ordialkyl tin dioxides) or a Lewis base such as dimethylaminopyridine(DMAP), and a suitable amount of toluene (or other water-azeotropeforming solvents) may be added to a reaction vessel and heated underazeotropic distillation conditions (e.g., refluxing using a Dean-Starkapparatus) until water is no longer removed from the reaction. Themixture may be cooled to room temperature, and the organic layer may beseparated, rinsed with water, dried, and purified.

The second chemical reaction depicted at the bottom of FIG. 6illustrates that the fourth bio-derived cross-linker having multipleacetate groups may be utilized to form a cross-linked polymeric materialvia a condensation cure reaction. As a prophetic example, ahydroxy-functionalized siloxane may be mixed with the fourth bio-derivedcross-linker having multiple acetate groups (1-50% w/w) and blended withexclusion of moisture. The blended mixture may be stored undermoisture-free conditions. The blended mixture may be applied to surfacesand materials and allowed to cure under atmospheric conditions.

FIG. 6 depicts an example in which all three acetate groups of thefourth bio-derived cross-linker react in the addition reaction.Depending on the reaction conditions, all three acetate groups may beused to cross-link the PDMS polymer or less than three acetate groupsmay be used for cross-linking. The ability to control the number ofacetate groups that react may enable better control of the mechanicalproperties of the final polymer.

Thus, FIG. 6 illustrates an example of a process of forming abio-derived cross-linker having multiple acetate groups fromhexane-1,3,4-triol (derived from the biorenewable moleculecis-3-hexenol) and utilizing the bio-derived cross-linker to form across-linked polymeric material via a condensation cure reaction. Thebio-derived cross-linker may be used to increase the biorenewablecontent of a resulting cross-linked polymeric material (e.g., across-linked PDMS material).

Referring to FIG. 7, a chemical reaction diagram 700 illustrates aparticular embodiment of a process of utilizing the bio-derivedhexane-1,3,4-triol molecule to form a fifth bio-derived cross-linker(identified as “Bio-Derived Cross-Linker(5)” in FIG. 7) that includesmultiple thiol (or mercapto) groups. FIG. 7 further illustrates that thebio-derived cross-linker may be utilized to form a cross-linkedpolymeric material (e.g., a cross-linked PDMS material), according toone embodiment.

The first chemical reaction depicted at the top of FIG. 7 illustratesthat the bio-derived hexane-1,3,4-triol molecule may be reacted withethyl mercaptoacetic acid via a condensation reaction (acid/basepromoted) to synthesize a cross-linker with multiple thiol (or mercpato)groups. The ethyl mercaptoacetic acid may be synthesized frombiorenewable acrylic acid via subsequent halogenation and substitutionreactions.

As a prophetic example, hexane-1,3,4-triol (1 equiv.),3-mercaptopropionic acid (4.5-5.0 equiv.), catalytic p-toluenesulfonicacid (or other catalysts such as sulfonic acids, triflic acid, sulfuricacid, phosphoric acid, hydrogen sulfates, dihydrogen phosphates,phosphonic acid esters, or dialkyl tin dioxides) or a Lewis base such asdimethylaminopyridine (DMAP), 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU),or triphenylphosphine, and a suitable amount of toluene (or otherwater-azeotrope forming solvents) may be added to a reaction vessel andheated under azeotropic distillation conditions (e.g., refluxing using aDean-Stark apparatus) until water is no longer removed from thereaction. The mixture may be cooled to room temperature, and the organiclayer may be separated, rinsed with water, dried, and purified.

The second chemical reaction depicted at the bottom of FIG. 7illustrates that the fifth bio-derived cross-linker may be utilized toform a cross-linked polymeric material via a thiol-ene cure reaction. Asa prophetic example, the fifth bio-derived cross-linker having multiplethiol groups (2-6% w/w) may be mixed with a vinyl-functionalizedsiloxane. The mixture may include a radical initiator, such as aMicheler's ketone, an alpha-amino-ketone, an alpha-hydroxy-ketone, abenzyldimethyl ketal, or benzophenone (among other alternatives). Themixture may be applied to molds or coated onto a substrate and curedunder UV light at a time and temperature suitable to the includedradical initiators as appropriate for desired applications.

FIG. 7 depicts an example in which all three thiol groups of the fifthbio-derived cross-linker react in the thiol-ene cure reaction. Dependingon the reaction conditions, all three thiol groups may be used tocross-link the PDMS polymer or less than three thiol groups may be usedfor cross-linking. The ability to control the number of thiol groupsthat react may enable better control of the mechanical properties of thefinal polymer.

Thus, FIG. 7 illustrates an example of a process of forming abio-derived cross-linker having multiple thiol (or mercapto) groups fromhexane-1,3,4-triol (derived from the biorenewable moleculecis-3-hexenol) and utilizing the bio-derived cross-linker to form across-linked polymeric material via a thiol-ene cure reaction. Thebio-derived cross-linker may be used to increase the biorenewablecontent of a resulting cross-linked polymeric material (e.g., across-linked PDMS material).

Referring to FIG. 8, a chemical reaction diagram 800 illustrates aparticular embodiment of a process of utilizing the biorenewablecis-3-hexenol molecule to form a sixth bio-derived cross-linker(identified as “Bio-Derived Cross-Linker(5)” in FIG. 8) that includesmultiple thiol (or mercapto) groups. FIG. 8 further illustrates that thebio-derived cross-linker may be utilized to form a cross-linkedpolymeric material (e.g., a cross-linked PDMS material), according toone embodiment.

The first chemical reaction depicted at the top of FIG. 8 illustratesthat the biorenewable cis-3-hexenol molecule may be utilized to form across-linker with multiple thiol (or mercapto) groups via a multiplestep reaction that includes the use of an acetate protected thiolbromopropane (commercially available) and substitution chemistry, thenremoving the protecting group. As a prophetic example, cis-3-hexenol maybe added to a suspension or solution of a base (e.g., sodium hydride) inan organic solvent, such as tetrahydrofuran (THF), diethyl ether, orN,N-dimethylformamide (DMF) at 0° C. The reaction mixture may be stirredfor 30 minutes before adding S-(3-bromopropyl)ethanethioic acid ester(>3 equiv.), dropwise. The reaction mixture may be stirred forapproximately 3 hours, and then neutralized by hydrochloric (HCl) acid.The aqueous and organic layers may then be separated. The aqueous layermay be extracted with diethyl ether, and rinsed with brine. The organiclayer may be dried over magnesium sulfate (MgSO₄), and the solvent maybe removed in vacuo. The residue may be purified by distillation orcolumn chromatography. The resultant product may be dissolved in DCM at0° C. and an acid such as trifluoroacetic acid may be added, dropwise.The reaction may be stirred for 3 hours at room temperature, and pouredinto water. The aqueous and organic layers may then be separated. Theaqueous layer may then be extracted with diethyl ether, and rinsed withbrine. The organic layer may be dried over magnesium sulfate (MgSO₄),and the solvent may be removed in vacuo. The residue is purified bydistillation or column chromatography.

The second chemical reaction depicted at the bottom of FIG. 8illustrates that the sixth bio-derived cross-linker may be utilized toform a cross-linked polymeric material via a thiol-ene cure reaction. Asa prophetic example, the sixth bio-derived cross-linker having multiplethiol groups (2-6% w/w) may be mixed with a vinyl-functionalizedsiloxane. The mixture may include a radical initiator, such as aMicheler's ketone, an alpha-amino-ketone, an alpha-hydroxy-ketone, abenzyldimethyl ketal, or benzophenone (among other alternatives). Themixture may be applied to molds or coated onto a substrate and curedunder UV light at a time and temperature suitable to the includedradical initiators as appropriate for desired applications.

FIG. 8 depicts an example in which all three thiol groups of the sixthbio-derived cross-linker react in the thiol-ene cure reaction. Dependingon the reaction conditions, all three thiol groups may be used tocross-link the PDMS polymer or less than three thiol groups may be usedfor cross-linking. The ability to control the number of thiol groupsthat react may enable better control of the mechanical properties of thefinal polymer.

Thus, FIG. 8 illustrates an example of a process of forming abio-derived cross-linker having multiple thiol (or mercapto) groups fromthe biorenewable molecule cis-3-hexenol and utilizing the bio-derivedcross-linker to form a cross-linked polymeric material via a thiol-enecure reaction. The bio-derived cross-linker may be used to increase thebiorenewable content of a resulting cross-linked polymeric material(e.g., a cross-linked PDMS material).

Referring to FIG. 9, a chemical reaction diagram 900 illustrates thatthe bio-derived cross-linkers having multiple thiol (or mercapto) groupsmay be joined together to form a polymeric network of disulfide bonds,according to one embodiment. In the example depicted in FIG. 9, thebio-derived cross-linker of FIG. 8 may undergo an oxidation-reductionreaction to form multiple disulfide linkages. While FIG. 9 illustratesan example in which the bio-derived cross-linker corresponds to theexample cross-linker depicted in FIG. 8, it will be appreciated that thebio-derived cross-linker of FIG. 7 that includes multiple thiol (ormercapto) groups) may also undergo a similar oxidation-reductionreaction to form a polymeric network of disulfide linkages.

Referring to FIG. 10, a flow diagram illustrates an example of a process1000 of forming a bio-derived cross-linker from biorenewablecis-3-hexenol (natural leaf alcohol), according to one embodiment. Inthe particular embodiment depicted in FIG. 10, the process 1000 alsoincludes utilizing the bio-derived cross-linker to form a cross-linkedpolymeric material.

The process 1000 includes forming a bio-derived cross-linker (e.g.,hexane-1,3,4-triol) by from biorenewable cis-3-hexenol, at 1002. Forexample, biorenewable cis-3-hexenol may be converted tohexane-1,3,4-triol according to the process described herein withrespect to FIG. 1 (e.g., via Sharpless Asymmetric Dihydroxylation). Asanother example, biorenewable cis-3-hexenol may be converted to thesixth bio-derived cross-linker according to the process described hereinwith respect to FIG. 8 (e.g., via a multi-step reaction).

In the particular embodiment depicted in FIG. 10, the process 1000 alsoincludes chemically reacting the bio-derived cross-linker with apolymeric material to form a cross-linked polymeric material, at 1004.For example, referring to FIG. 1, the first cross-linked PDMS materialmay be formed from a hydride-functionalized siloxane and the bio-derivedhexane-1,3,4-triol via a condensation cure reaction. As another example,referring to FIG. 2, the second cross-linked PDMS material may be formedfrom an alkoxy-functionalized (e.g., methoxy-functionalized) siloxaneand the bio-derived hexane-1,3,4-triol via a condensation cure reaction.As yet another example, referring to FIG. 8, the eighth cross-linkedPDMS material may be formed from a vinyl-functionalized siloxane and thesixth bio-derived cross-linker via a thiol-ene cure reaction.

Thus, FIG. 10 illustrates an example of a process of forming abio-derived cross-linker (e.g., hexane-1,3,4-triol) from biorenewablecis-3-hexenol (natural leaf alcohol) and utilizing the bio-derivedcross-linker to form a cross-linked polymeric material (e.g., across-linked PDMS material).

Referring to FIG. 11, a flow diagram illustrates an example of a processof forming a bio-derived cross-linker from biorenewable cis-3-hexenol(natural leaf alcohol), according to one embodiment. In FIG. 11, thebio-derived hexane-1,3,4-triol molecule is formed from biorenewablecis-3-hexenol and is subsequently chemically reacted with one or moreother biorenewable materials to form bio-derived cross-linkers withdifferent functional groups. In the particular embodiment depicted inFIG. 11, the process 1100 also includes utilizing the bio-derivedcross-linker to form a cross-linked polymeric material.

The process 1100 includes forming bio-derived hexane-1,3,4-triol frombio-derived cis-3-hexenol, at 1102. For example, biorenewablecis-3-hexenol may be converted to hexane-1,3,4-triol according to theprocess described herein with respect to FIG. 1 (e.g., via SharplessAsymmetric Dihydroxylation).

The process 1100 also includes converting the bio-derivedhexane-1,3,4-triol to a bio-derived cross-linker via one or morechemical reactions with one or more biorenewable materials, at 1104. Forexample, referring to FIG. 3, the bio-derived hexane-1,3,4-triol may beutilized to form a bio-derived cross-linker having multiple acrylategroups. As another example, referring to FIGS. 4 and 5, the bio-derivedhexane-1,3,4-triol may be utilized to form bio-derived cross-linkershaving multiple vinyl groups. As another example, referring to FIG. 6,the bio-derived hexane-1,3,4-triol may be utilized to form a bio-derivedcross-linker having multiple acetate groups. As yet another example,referring to FIG. 7, the bio-derived hexane-1,3,4-triol may be utilizedto form bio-derived cross-linkers having multiple thiol (or mercapto)groups.

The process 1100 further includes chemically reacting the bio-derivedcross-linker with a polymeric material to form a cross-linked polymericmaterial, at 1106. For example, referring to FIG. 3, the thirdcross-linked PDMS material may be formed from a hydride-functionalizedsiloxane and the second bio-derived cross-linker (having multipleacrylate groups) via an addition reaction. As another example, referringto FIGS. 4 and 5, the third bio-derived cross-linker (having multiplevinyl groups) may be used to form a cross-linked PDMS material via aperoxide cure reaction or via a condensation cure reaction. As a furtherexample, referring to FIG. 6, the sixth cross-linked PDMS material maybe formed from a hydroxy-functionalized siloxane and the fourthbio-derived cross-linker (having multiple acetate groups) via acondensation cure reaction. As yet another example, referring to FIGS. 7and 8, the fifth and sixth bio-derived cross-linkers (having multiplethiol/mercapto) groups may be used to form a cross-linked PDMS materialvia a thiol-ene cure reaction.

Thus, FIG. 11 illustrates an example of a process of forminghexane-1,3,4-triol from biorenewable cis-3-hexenol (natural leafalcohol), utilizing the bio-derived hexane-1,3,4-triol to form abio-derived cross-linker with alternative functional groups, andutilizing the bio-derived cross-linker to form a cross-linked polymericmaterial (e.g., a cross-linked PDMS material).

It will be understood from the foregoing description that modificationsand changes may be made in various embodiments of the present inventionwithout departing from its true spirit. The descriptions in thisspecification are for purposes of illustration only and are not to beconstrued in a limiting sense. The scope of the present invention islimited only by the language of the following claims.

1.-20. (canceled)
 21. A process of forming a cross-linkedpolydimethylsiloxane (PDMS) material, the process comprising utilizinghexane-1,3,4-triol as a bio-derived cross-linker to form thecross-linked PDMS material.
 22. The process of claim 21, furthercomprising forming the hexane-1,3,4-triol from biorenewablecis-3-hexenol.
 23. The process of claim 21, wherein the cross-linkedPDMS material is formed via a chemical reaction of ahydride-functionalized PDMS material and hexane-1,3,4-triol.
 24. Theprocess of claim 21, wherein the cross-linked PDMS material is formedvia a chemical reaction of an alkoxy-functionalized PDMS material andhexane-1,3,4-triol.
 25. The process of claim 24, wherein thealkoxy-functionalized PDMS material includes a methoxy-functionalizedPDMS material.
 26. A process of forming a cross-linkedpolydimethylsiloxane (PDMS) material, the process comprising utilizing ahexane-1,3,4-triol derivative as a bio-derived cross-linker to form thecross-linked PDMS material.
 27. The process of claim 26, furthercomprising: forming hexane-1,3,4-triol from biorenewable cis-3-hexenol;and forming the hexane-1,3,4-triol derivative from thehexane-1,3,4-triol.
 28. The process of claim 26, wherein thehexane-1,3,4-triol derivative includes multiple acrylate groups.
 29. Theprocess of claim 26, wherein the hexane-1,3,4-triol derivative includesmultiple vinyl groups.
 30. The process of claim 26, wherein thehexane-1,3,4-triol derivative includes multiple acetate groups.
 31. Theprocess of claim 26, wherein the hexane-1,3,4-triol derivative includesmultiple thiol groups.
 32. The process of claim 26, wherein utilizingthe hexane-1,3,4-triol derivative as the bio-derived cross-linker toform the cross-linked PDMS material includes chemically reacting thehexane-1,3,4-triol derivative with a functionalized PDMS material. 33.The process of claim 32, wherein the hexane-1,3,4-triol derivativeincludes multiple acrylate groups, and wherein the functionalized PDMSmaterial includes a hydride-functionalized PDMS material.
 34. Theprocess of claim 32, wherein the hexane-1,3,4-triol derivative includesmultiple vinyl groups, and wherein the functionalized PDMS materialincludes a vinyl-functionalized PDMS material.
 35. The process of claim32, wherein the hexane-1,3,4-triol derivative includes multiple acetategroups, and wherein the functionalized PDMS material includes ahydoxy-functionalized PDMS material.
 36. The process of claim 32,wherein the hexane-1,3,4-triol derivative includes multiple thiolgroups, and wherein the functionalized PDMS material includes avinyl-functionalized PDMS material.
 37. The process of claim 36, whereinthe hexane-1,3,4-triol derivative that includes multiple thiol groupshas the following chemical structure:


38. A process of forming a cross-linked polymeric material, the processcomprising: utilizing biorenewable cis-3-hexenol to form a bio-derivedcross-linker that includes multiple thiol groups; and utilizing thebio-derived cross-linker to form a cross-linked polymeric material thatincludes a polymeric network of disulfide linkages.
 39. The process ofclaim 38, wherein the bio-derived cross-linker that includes multiplethiol groups has the following chemical structure:


40. The process of claim 38, wherein the bio-derived cross-linker thatincludes multiple thiol groups undergoes an oxidation-reduction reactionto form the polymeric network of disulfide linkages.